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WO2013018951A1 - Polymère conducteur comprenant du 3,6-carbazole et pile photovoltaïque organique l'utilisant - Google Patents

Polymère conducteur comprenant du 3,6-carbazole et pile photovoltaïque organique l'utilisant Download PDF

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WO2013018951A1
WO2013018951A1 PCT/KR2011/006322 KR2011006322W WO2013018951A1 WO 2013018951 A1 WO2013018951 A1 WO 2013018951A1 KR 2011006322 W KR2011006322 W KR 2011006322W WO 2013018951 A1 WO2013018951 A1 WO 2013018951A1
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solar cell
heteroaryl
aryl
alkyl
copolymer
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PCT/KR2011/006322
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Korean (ko)
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박태호
이강영
임민정
송슬기
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포항공과대학교 산학협력단
주식회사 엘지화학
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Priority to US14/235,731 priority Critical patent/US20140318625A1/en
Publication of WO2013018951A1 publication Critical patent/WO2013018951A1/fr

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Definitions

  • the present invention relates to a conductive polymer containing 3,6-carbazole and an organic solar cell device using the same as a photoelectric conversion material. More specifically, the hole mobility is improved by adding a certain amount of 3,6-carbazole to the conductive polymer.
  • the present invention relates to an organic solar cell apparatus which manufactures a conductive polymer and improves energy conversion efficiency by using the same as a photoelectric conversion material.
  • the electron-hole pair moves to the interface between the copolymer and the C60 fullerene derivative or the C70 fullerene derivative and is separated into electrons and holes, and then electrons are moved to the metal electrode and holes are moved to the transparent electrode to generate electrons.
  • the efficiency of organic polymer thin film solar cells using organic polymers is 6.5-7.0% (Science, 2007, 307, 222-225).
  • Korean Patent Publication No. 2010-0111767 discloses a conductive polymer in which 2,7-carbazole is included in a main chain and an organic solar cell using the same.
  • the conductive polymer containing 2,7-carbazole in the main chain is to improve light absorption and hole mobility to improve the efficiency of the solar cell.
  • the hole mobility is relatively low compared to the electron mobility, and thus there is a problem in that light efficiency is not easily improved.
  • the problem to be solved in the present invention is to provide a new conductive copolymer that can be produced a solar cell of high efficiency because the mobility of the major is similar to the mobility of the electron.
  • Another problem to be solved by the present invention is to provide a solar cell having a high efficiency similar to the mobility of the electron and a manufacturing method thereof.
  • Another problem to be solved by the present invention is to provide a high efficiency photoelectric conversion device and a method of manufacturing the same, the mobility of the major electron mobility is correspondingly high.
  • the present invention provides a copolymer containing a 3,6-carbazole group represented by the following formula (1).
  • Y is an electron acceptor
  • X is an electron donor
  • m is more preferably 0.01 ⁇ m ⁇ 0.7, more preferably 0.01 ⁇ m ⁇ 0.5, and most preferably 0.01 ⁇ m ⁇ 0.1.
  • the copolymer of Formula 1 is a 3,6-carbazole and an electron acceptor having a high hole mobility as a second electron donor in an electron acceptor (Y) -electron donor (X) bond structure as a conductive copolymer.
  • Y The coupling structure is irregularly arranged.
  • the electron acceptor (Y) and the electron donor (X) may use a conventional electron acceptor and an electron donor known in the organic solar cell.
  • the electron acceptor Y is a C 10 or more carbon-based aromatic or sulfur, phosphorus, nitrogen, selenium is an aromatic compound containing selenium may have a substituent that can increase the solubility of the polymer.
  • the electron acceptor (Y) may be used alone or in combination of two or more of the compounds represented by the following general formula (2).
  • R 4 or R 5 is C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 3 -C 20 cycloalkyl, C 1 -C 20 heterocycloalkyl, aryl, heteroaryl, CN, C (O) R, C (O) OR, wherein R is C 1 -C 20 alkyl, C 1 -C 20 heterocycloalkyl, aryl, heteroaryl.
  • the electron donor X is preferably one or two or more of the compounds represented by the following general formula (3).
  • R 2 or R 3 is C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 3 -C 20 cycloalkyl, C 1 -C 20 heterocycloalkyl, C 1 -C 20 aryl, C 1 -C 20 heteroaryl, CN, C (O) R, C (O) OR, wherein R is C 1 -C 20 alkyl, C 1 -C 20 heterocycloalkyl, C 1 -C 20 aryl, C 1 -C 20 Heteroaryl.
  • the present invention is to provide an organic solar cell using a conductive copolymer having a 3,6-carbazole group.
  • the organic solar cell may be composed of a substrate, a first electrode, a photoelectric conversion layer and a second electrode
  • a conductive polymer containing a 3,6-carbazole group represented by Formula 1 may be used as an electron donor, and a C60 fullerene derivative or a C70 fullerene derivative may be incorporated as an electron acceptor.
  • a buffer layer may be further introduced between the first electrode, and an electron transport layer, a hole blocking layer, or an optical space layer may be further introduced between the photoconversion layer and the second electrode.
  • the substrate is preferably a transparent material, and examples thereof include glass or polyethylene terephthalate (PET), polyethylene naphthelate (PEN), polypropylene (PP), polyamide (PI), triacetyl cellulose (TAC), and the like.
  • the first electrode may be formed on one surface of the substrate by applying a transparent material or coating in the form of a film using a method such as sputtering or spin coating.
  • the first electrode is a part that functions as an anode, and may be used without particular limitation as long as it has a transparency and conductivity as a material having a lower work function than the second electrode. Examples of preferred examples thereof include indium-tin oxide (ITO) and FTO.
  • the buffer layer formed on top of the first electrode may use poly (3,4-ethylenedioxythiophene) [PEDOT: PSS] doped with polystyrenesulfonate, and may be introduced to further improve hole mobility. have.
  • the photoelectric conversion material of the photoelectric conversion layer is that the mixing ratio of the conductive polymer containing a 3,6-carbazole group represented by the formula (1) and the C60 fullerene derivative or C70 fullerene derivative in a weight ratio of 1: 0.5 to 1: 4 desirable.
  • the fullerene derivative when the fullerene derivative is blended in less than 0.5 weight ratio, the content of the crystallized fullerene derivative is insufficient, resulting in the interference of the generated electrons, and when the weight ratio exceeds 4 weight ratio, Since the amount of the conductive polymer that absorbs light is relatively reduced, efficient absorption of light is not achieved, which is undesirable.
  • the solution in which the photoelectric conversion material is dissolved is applied or coated by one method selected from spin coating, screen printing, inkjet printing, and doctor blade methods, and has a thickness of about 70 nm or more, preferably 80 to 200 nm. It is formed of a photoelectric conversion layer.
  • the second electrode may be stacked on top of the photoelectric conversion layer by vacuum thermal evaporation of a metal material such as aluminum to 100-200 nm under vacuum in the state where the photoelectric conversion layer is introduced.
  • Materials that can be used as the second electrode are gold, aluminum, copper, silver or alloys thereof, calcium / aluminum alloys, magnesium / silver alloys, and the like.
  • the present invention is an organic photovoltaic device, an organic light emitting device comprising a conductive polymer containing a 3,6-carbazole group represented by Formula 1 and an electron acceptor such as C60 fullerene derivative or C70 fullerene derivative
  • a photoelectric conversion material for a diode or an organic thin film transistor is provided.
  • the present invention can first increase the efficiency of the device by adding a small amount of 3,6-carbazole having good hole mobility to all the conductive polymers used in various types of conventional photoelectric conversion device.
  • the conductive polymer in which the carbazole compound of the present invention is introduced can be used as an electron donor in an organic photovoltaic device, and used in various fields of organic electronic materials such as organic thin film transistor (OTFT) and organic light emitting diode (OLED). It can be useful.
  • organic thin film transistor OTFT
  • OLED organic light emitting diode
  • the present invention provides an organic photovoltaic device using a conductive polymer in which a carbazole compound is introduced as an electron donor, thereby achieving high photoelectric conversion efficiency of an organic thin film solar cell.
  • 1 is a hole conductivity comparison graph according to an embodiment of the present invention.
  • FIG. 2 is a current-voltage graph according to an embodiment of the present invention.
  • 3 is a graph comparing electron-hole mobility according to an embodiment of the present invention.
  • the reaction is carried out at 85 ° C. for 48 hours. After the polymerization, the mixture was polymerized with phenylboronic acid (10 mg) and bromobenzene (1 ml). The reaction was poured into methanol (200 ml), the precipitate was filtered off and extracted with acetone and nucleic acid chloroform to obtain 95.2 mg of product polymer 1.
  • the obtained material was measured for the hole mobility of Product 1 and Product 2 by Space Charge Limited Current (SCLC), respectively.
  • the measured hole mobility was 1.2 ⁇ 10 ⁇ 5 cm 2 V ⁇ 1 s ⁇ 1 for polymer 1 and 3.2 ⁇ 10 ⁇ 6 cm 2 V ⁇ 1 s ⁇ 1 for polymer 2.
  • FIG. 1 which shows the hole mobility of the polymer 1 and the polymer 2
  • the polymer 1 has a hole conductance about 10 times larger than that of the polymer 2.
  • the reaction is carried out at 110 ° C. for 2 hours in a microreactor.
  • polymerization was carried out with phenyl boronic acid (10 mg) and bromobenzene (1 ml).
  • the reaction was poured into methanol (200 ml), the precipitate was filtered off and extracted with acetone and nucleic acid chloroform to give 220 mg (99%) of a dark purple solid.
  • An organic photovoltaic device was fabricated using the material shown above as the active layer. First, the substrate on which the indium tin oxide layer is laid is wiped with a cotton swab using 2-propanol, and then washed with an ultrasonic mill for 15 minutes in order of ethanol, acetone, and 2-propanol. Thereafter, the treatment was performed for about 120 seconds using an ozone / ultraviolet device.
  • PEDOT PSS (poly (3,4-ethylene dioxythiophene) -poly (4-styrenesulfonate)) polymer and 2-propanol were mixed and filtered at a ratio of 1: 2, followed by 60 seconds in a spin coater. Was deposited at 4000 rpm and then dried in an oven at 150 ° C. for 10 minutes.
  • PSS poly (3,4-ethylene dioxythiophene) -poly (4-styrenesulfonate)
  • Examples 1 to 4 (polymer 3 to polymer 6) prepared by containing 3,6 carbazole do not contain 3,6-carbazole Comparative Example 1 (polymer 7) The efficiency is 88%, 96%, 65% and 57%, respectively.
  • the reaction is carried out at 85 ° C. for 48 hours. At the end of the polymerization, polymerize with phenyl boronic acid (10 mg) and bromobenzene (1 ml). The reaction was poured into methanol (200 ml), the precipitate was filtered off and extracted with acetone and nucleic acid chloroform to give 148 mg of P1.
  • the catalyst tetrakis (triphenylphosphine) palladium (0) (5 mg) and four drops of Aliquat 336 were added and reacted at 110 ° C. for 2 hours in a microreactor. A dark purple solid powder (221 mg) was obtained.
  • the reaction is carried out at 85 ° C. for 48 hours. At the end of the polymerization, polymerize with phenylboronic acid (10 mg) and bromobenzene (1 ml). The reaction was poured into methanol (200 ml), the precipitate was filtered off and extracted with acetone and nucleic acid chloroform to give 256 mg of polymer 9.
  • the catalyst tetrakis (triphenylphosphine) palladium (0) (5 mg) and four drops of Aliquat 336 were added and reacted at 110 ° C. for 2 hours in a microreactor. A dark purple solid powder (221 mg) was obtained.
  • Example 5 (polymer 9), Example 6 (polymer 11), Comparative Example 3 (polymer 8), Comparative Example 4 (polymer 10) material presented above
  • the organic photovoltaic device was manufactured using the as an active layer. Jsc, Voc, FF, PEC were measured for the prepared device and are shown in Table 3 below.
  • Example 6 (polymer 9) and Example 7 (polymer 10) containing a small amount of 3,6-carbazole
  • Comparative Example 3 (polymer 8) does not contain 3,6-carbazole
  • Comparative Example 4 (polymer 10) the efficiency was improved by 20% and 23%, respectively.

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  • Spectroscopy & Molecular Physics (AREA)
  • Photovoltaic Devices (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

La présente invention concerne un polymère conducteur contenant un groupe 3,6-carbazole représenté par la formule chimique 1, ainsi qu'une pile photovoltaïque à couches minces d'un polymère organique. Dans la formule chimique 1, Y représente un accepteur d'électrons et X un donneur d'électrons. R1 représente un alkyle en C1 à C20, un alcoxy en C1 à C20, un cycloalkyle en C1 à C20, un hétérocycloalkyle en C1 à C20, un aryle, un hétéroaryle, CN, C(O)R, et C(O)OR, où R représente l'alkyle en C1 à C20, l'hétérocycloalkyle en C1 à C20, l'aryle et l'hétéroaryle. 1 et m sont tels que 1 + m = 1 en termes de fraction molaire et m est tel que 0,01 ≤ m ≤ 0,9. n est égal à 5 à 200 en termes de degré de polymérisation. Le polymère conducteur contenant le groupe 3,6-carbazole selon la présente invention peut permettre l'obtention d'une pile photovoltaïque organique à couches minces présentant une très bonne conductivité de type P et un très bon effet photovoltaïque, ainsi qu'une très bonne efficacité de conversion de la lumière en électricité, car il peut être appliqué sur un élément par une technique de dépôt par rotation.
PCT/KR2011/006322 2011-08-03 2011-08-26 Polymère conducteur comprenant du 3,6-carbazole et pile photovoltaïque organique l'utilisant WO2013018951A1 (fr)

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KR101687807B1 (ko) 2014-10-27 2017-01-02 주식회사 엘지화학 유기 태양전지용 잉크 조성물 및 이를 이용한 유기 태양전지 제조방법
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KR20160141683A (ko) 2016-09-21 2016-12-09 (주)노터스생명과학 Tlr7 항진제를 포함하는 비만 또는 간질환 예방 및 치료용 약학 조성물
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KR101902129B1 (ko) 2017-05-24 2018-09-28 주식회사 엘지화학 헤테로환 화합물 및 이를 포함하는 유기 전자 소자
KR102626760B1 (ko) * 2020-11-23 2024-01-19 한국과학기술원 유기 태양전지용 고분자 공여체 및 이를 포함하는 유기 태양전지
US12258441B1 (en) * 2024-05-24 2025-03-25 Imam Mohammad Ibn Saud Islamic University Fabrication of a conjugated polymer

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US20130032209A1 (en) 2013-02-07
US20140318625A1 (en) 2014-10-30
US8921506B2 (en) 2014-12-30
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